BR112018014372B1 - COMPOSITE ARTICLE, METHOD FOR FORMING A COMPOSITE ARTICLE, AND, SUBMARINE STRUCTURE - Google Patents

Abstract

A composite article includes a low surface energy polymer layer, a poly(meth)acrylate layer, an epoxide layer and a hydrolytically resistant layer. The poly(meth)acrylate layer is arranged in and in direct contact with the polymer layer with low surface energy and includes the reaction product of at least one acrylate which is polymerized in the presence of an organoborane initiator such that the poly(meth)acrylate includes boron. The epoxy layer is arranged on and in direct contact with the poly(meth)acrylate layer. The hydrolytically resistant layer is disposed in and in direct contact with the epoxide and is the reaction product of an isocyanate component and an isocyanate-reactive component reacted in the presence of a curing agent. The isocyanate-reactive component includes a polydiene polyol and the curing agent cross-links the carbon-carbon double bonds of the polydiene polyol.

Description

CROSS REFERENCE TO RELATED ORDERS

[001] This order claims priority to Provisional Order No. US 62/279,033, filed January 15, 2016; to US Provisional Order No. 62/279,027, filed on January 15, 2016; to US Provisional Order No. 62/279,026, filed on January 15, 2016; and US Provisional Order No. 62/279,029, filed January 15, 2016, the contents of each being incorporated herein by reference in their entirety.

DESCRIPTION FIELD

[002] The present description generally relates to a composite article and a method of forming the composite article. More particularly, the composite article includes a low surface energy polymer, a poly(meth)acrylate, an epoxide and a hydrolytically resistant layer. The composite article can be used in subsea applications such as for use in subsea pipelines and other subsea structures.

FUNDAMENTALS

[003] Domestic energy needs currently exceed easily accessible energy resources, forcing an increasing dependence on foreign petroleum fuels such as oil and gas. At the same time, existing energy resources are significantly underutilized, in part due to inefficient methods of finding and obtaining oil and gas.

[004] Petroleum fuels, such as oil and gas, are typically sought and obtained from underground reservoirs through a borehole that is drilled by a rig. In offshore oil and gas exploration ventures, subsurface reservoirs are below the ocean floor. To access petroleum fuels, the rig drills the ocean floor down to approximately one or two miles (1.6 to 3.2 km) below the ocean floor. Various pipelines and subsea structures are used to transport petroleum fuels from this depth below the ocean floor to above the ocean surface and particularly to an oil platform located on the ocean surface. These underwater pipelines and other structures can be made from a metallic material or a combination of metallic materials. Petroleum fuels such as oil originating at a depth of about one to two miles (1.6 to 3.2 km) below the ocean floor are very hot (eg, around 130°C). In contrast, at this depth, seawater is very cold (eg around 4°C). This vast temperature difference requires that the various subsea pipelines and structures be insulated to maintain the relatively high temperature of petroleum fuels so that fuels such as oil and gas can flow easily through subsea pipelines and other subsea structures. Generally, if the fuel, such as oil, gets too cold due to the temperature of the seawater, it will become too viscous to flow through pipelines and other structures and will not be able to reach the ocean surface and/or oil rig. Even in cases where fuel can flow, fuel can flow very slowly to reach the ocean surface and/or oil platform in an efficient time frame for the desired operating conditions. Alternatively and/or additionally, the fuel can form waxes that act harmfully to clog pipes and structures. Furthermore, due to the cold temperature of the sea water, the fuel can form hydrates which harmfully change the nature of the fuel and can also clog the pipes and structures.

[005] In other examples, pipelines can be as long as 50 miles (80 km) and can be either above water or below water. When traveling such distances, the fuel is exposed to many changes in temperature. To complicate these cases, the fuel must also travel, in pipelines, 50 miles (80 km) through these temperature changes and one to two miles (1.6 to 3.2 km) below the ocean floor to the oil above the ocean surface, without losing its integrity. For example, the fuel may need to be of low viscosity to remain fluent over these distances and may need to be properly uniform, eg without harmful hydrates and waxes.

[006] In view of these types of problems, subsea structures are typically constructed by lining a central tube or insulated passage. However, during construction, the ends of structures are typically not insulated to allow welding or other connections to be made to extend the length of the structures. For this reason, subsea structures must be patched after welding with a polymer to ensure continuity of insulation and overall integrity. However, in many cases, the strength of adhesion (or removal) of the adhesive applied to the substrate is weak, as is the resistance to hydrolysis of the resulting adhesive. Consequently, an opportunity for improvement remains.

SUMMARY OF DESCRIPTION

[007] The present description describes a composite article having a first layer including a low surface energy polymer, a poly(meth)acrylate layer disposed on and in direct contact with said first layer, an epoxy layer disposed on and in direct contact with said poly(meth)acrylate layer, and a hydrolytically resistant layer disposed over and in direct contact with said epoxide layer. The poly(meth)acrylate layer includes the reaction product of at least one (meth)acrylate which is polymerized in the presence of an organoborane initiator. The hydrolytically resistant layer includes a hydrolytically resistant polyurethane elastomer and is the reaction product of an isocyanate component and an isocyanate-reactive component which has reacted in the presence of a curing agent. The isocyanate-reactive component includes a polydiene polyol having an average hydroxy functionality of not more than about 3 and a number average molecular weight of from about 1000 to less than about 3000 g/mol. The curing agent cross-links the carbon-carbon double bonds of the polydiene polyol. The hydrolytically resistant layer has an initial tensile strength, as measured in accordance with standard test method DIN 53504 S2, and wherein said hydrolytically resistant layer retains at least 80% of said initial tensile strength, measured in accordance with the test method DIN 53504 S2 and after submersion in standardized seawater for at least 24 weeks at 102°C in accordance with ASTM D665.

[008] The present description also provides for the related subsea structures, including the composite articles, as well as the associated method for forming the composite articles.

BRIEF DESCRIPTION OF THE DRAWINGS

[009] Other advantages of the present description will be readily noted, as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings, in which: Figure 1 is a perspective view of a subsea tube including a first layer including a low surface energy polymer; Figure 2 is a perspective view of a subsea structure that includes an embodiment of the multi-layer coating of this description; Figure 3 is a side cross-section of one embodiment of the composite article of this description; and Figure 4 is a graph comparing the change in tensile strength of elastomeric polyurethane sheets for the number of immersion weeks.

DETAILED DESCRIPTION DESCRIPTION

[0010] The present description includes a composite article (10). The composite article (10) typically includes four layers stacked on top of each other, as shown in Figure 3. In various embodiments, the composite article (10) includes, is, consists of, or essentially consists of a first layer ( 14), a poly(meth)acrylate layer (16), an epoxide layer (18), and a hydrolytically resistant layer (20). The first layer (14) includes, is, consists of, or essentially consists of a polymer that has a low surface energy. The first layer (14) can be described as a polymer layer. The poly(meth)acrylate layer (16) includes, is, consists of, or essentially consists of a poly(meth)acrylate. The epoxide layer (18) includes, is, consists of, or essentially consists of an epoxide. The hydrolytically resistant layer (20) can be described as a hydrolytically resistant polymer layer. The hydrolytically resistant layer (20) includes, is, consists of, or essentially consists of a hydrolytically resistant layer. In certain embodiments, the hydrolytically resistant layer (20) includes, is, consists of, or essentially consists of a hydrolytically resistant polyurethane elastomer layer. The poly(meth)acrylate layer (16), the epoxide layer (18), and the hydrolytically resistant layer (20) can be described as additional layers, such as second, third or fourth layers, etc. In various embodiments, the first layer (14) is described as an outermost first layer (22). In other embodiments, the hydrolytically resistant layer (20) is described as a second (e.g., outermost) layer (24). In still other embodiments, the poly(meth)acrylate layer (16) and the epoxide layer (18) are each described as a second and/or third layer. Each of these layers is described in more detail below. The terminology "consists essentially of" above describes embodiments that may be free of extraneous polymers or monomers that are reacted to form polymers. Regarding the composite article (10) itself, the terminology “consists essentially of” can describe modalities that are free of additional layers, for example, as full layers or as partial layers.

[0011] The composite article (10) typically has increased peel strength (i.e., peel strength at 90°), for example, compared to a composite article (10) which is free of the (meth)acrylate layer and/or or the epoxide layer (18). In various embodiments, the composite article (10) has a 90° peel strength (which may be a medium or median peel strength) of at least 55, 60, 65, 70, 75, 80, 85, 90, 95 , 100, 55 to 100, 60 to 95, 65 to 85, 70 to 80, 75 to 80, or 80 to 85 pli (pounds per linear inch, with 1 pound per linear inch corresponding to 0.1786 kg per linear cm) measured using ASTM D6862. Typically, these values are reported as an average peel strength.

[0012] In alternative modalities, all values and ranges of values between the above mentioned values are expressly contemplated here.

[0013] Peeling resistance can be measured between many different layers. For example, the aforementioned peel strength can be measured between the hydrolytically resistant layer (20) and the epoxide layer (18). Alternatively, peel strength can be measured between the hydrolytically resistant layer (20) and the poly(meth)acrylate layer (16) or the hydrolytically resistant layer (20) and the first layer (14). The peel strength is related to the type of failure of the composite article (10) when force is applied. For example, when peel strength is measured, the hydrolytically resistant layer (20) may begin to peel from another layer, for example the epoxide layer (18). Alternatively, when the peel strength is measured, the hydrolytically resistant layer (20) may tear/pull away from the composite article (10) and, for example, the epoxide layer (18). This is typically described in the art as cohesive failure. Typically, cohesive failure is preferred. First layer (14):

[0014] The first layer (14) of the composite article (10) may include, consist essentially of, or consist of a low surface energy polymer. The terminology "low surface energy" typically describes a polymer that has a surface energy of less than about 40 mN/m (milli-Newtons per meter), as determined at 20°C by ASTM D7490-13.

[0015] In various embodiments, the low surface energy polymer is chosen from polyethylene, polypropylene and combinations thereof. In still other embodiments, the low surface energy polymer is chosen from those listed immediately below and combinations thereof.

[0016] The first layer (14) may be an outermost layer of the composite article (10) or may be an inner layer of a larger article. If an outermost layer, the first layer (14) is free from contact with any other layer on an outer side and faces the environment on that side.

[0017] The first layer (14) is not limited to any particular dimension or thickness. In various embodiments, the first layer (14) has a thickness of 0.1 inch to 1 foot or more (with 1 inch equals about 2.54 cm and where 1 foot equals about 30.48 cm) . In various embodiments, the thickness is from 0.25 to 6 inches, from 0.25 to 3 inches, from 0.25 to 1 inch, from 0.25 to 0.75, or from 0.25 to 0.5, inches (with 1 inch equaling about 2.54 cm). In various non-limiting embodiments, all values and ranges of values between the aforementioned values are expressly contemplated herein.

Poly(meth)acrylate layer (16):

[0018] The composite article (10) also includes the poly(meth)acrylate layer (16). The poly(meth)acrylate layer (16) is disposed on and in direct contact with the first layer (14). In other words, there is no intermediate layer or bonding layer disposed between the poly(meth)acrylate layer (16) and the first layer (14). The poly(meth)acrylate layer (16) may include, consist essentially of, or consist of, a poly(meth)acrylate.

[0019] The poly(meth)acrylate itself may include, consist essentially of, or consist of, the reaction product of at least one acrylate that is polymerized in the presence of an organoborane initiator. The terminology "consists essentially of" describes an embodiment that is free of polymers or monomers that are reacted to form polymers. At least one acrylate may be a single acrylate, two acrylates, three acrylates, etc., each of which may independently be an acrylate or a methacrylate (collectively known as (meth)acrylate). (meth)acrylate can be described as a (meth)acrylate that has 3 to 20 carbon atoms, for example 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, carbon atoms or any range of values. In other embodiments, the (meth)acrylate is chosen from hydroxypropyl methacrylate, 2-ethylhexyl acrylate, acrylic acid, and combinations thereof. In other embodiments, the (meth)acrylate is chosen from 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, methyl acrylate, methyl methacrylate, butyl acrylate, ethyl acrylate, hexyl acrylate, butyl, butyl methacrylate, ethyl methacrylate, isooctyl acrylate, decyl acrylate, dodecyl acrylate, vinyl acrylate, acrylic acid, methacrylic acid, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, tetrahydrofurfuryl methacrylate, caprolactone acrylate, perfluorobutyl acrylate, perfluorobutyl methacrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl methacrylate, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, allyl acrylate, methacrylate allyl, stearyl acrylate, stearyl methacrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol diacrylate, di-dimethacrylate ethylene glycol, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, tetrahydroperfluoroacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, bisphenol A acrylate, bisphenol A dimethacrylate, ethoxylated bisphenol A acrylate, ethoxylated bisphenol A methacrylate, bisphenol A hexafluoro diacrylate, bisphenol A hexafluoro dimethacrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, N-isopropyl acrylamide, N,N-dimethyl acrylamide, t-octyl acrylamide, cyanoethyl acrylates, diacetone acrylamide, N-vinyl acetamide, N-vinyl formamide, polypropylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythrethacrylate tetraacrylate l, and combinations thereof. At least one (meth)acrylate may include only acrylate or methacrylate functionality. Alternatively, the at least one (meth)acrylate may include acrylate functionality and methacrylate functionality.

[0020] In various embodiments, the at least one (meth)acrylate is chosen from acrylates and monofunctional methacrylate esters and substituted derivatives thereof, such as cyano, chlorine, amino and silane derivatives as well as mixtures of acrylate and monofunctional substituted and unsubstituted methacrylates. In other embodiments, the at least one (meth)acrylate is chosen from low molecular weight methacrylate esters and amides such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methoxy ethyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, N,N-dimethyl methacrylamide and mixtures thereof. In still other embodiments, the at least one (meth)acrylate is chosen from methyl acrylate, ethyl acrylate, isobornyl methacrylate, butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate , decyl methacrylate, dodecyl methacrylate, tert-butyl methacrylate, acrylamide, N-methyl acrylamide, diacetone acrylamide, N-tert-butyl acrylamide, N-tert-octyl acrylamide, N-decyl methacrylamide, gamma-methacryloxypropyl trimethoxysilane, acrylate of 2-cyanoethyl, 3-cyanopropyl acrylate, tetrahydrofurfuryl chloroacrylate, glycidyl acrylate, glycidyl methacrylate, and the like. In other embodiments, the at least one (meth)acrylate is chosen from alkyl acrylates having 4 to 10 carbon atoms in the alkyl group, such as mixtures of methyl methacrylate and butyl acrylate. In still other embodiments, the at least a (meth)acrylate is chosen from hexanediol diacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, glycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, as well as other polyether diacrylates and dimethacrylates.

em que R e R’ são, cada, hidrogênio ou radicais orgânicos, e X é oxigênio. Misturas de (met) monômeros acrílicos também podem ser usadas. O pelo menos um (met)acrilato pode ser monofuncional, polifuncional ou uma combinação dos mesmos.[0021] In additional embodiments, the at least one (meth)acrylate has the formula:

wherein R and R' are each hydrogen or organic radicals, and X is oxygen. Mixtures of (met) acrylic monomers can also be used. The at least one (meth)acrylate may be monofunctional, polyfunctional or a combination thereof.

[0022] The at least one (meth)acrylate is polymerized in the presence of an organoborane initiator to form the poly(meth)acrylate. This polymerization typically results in the poly(meth)acrylate including amounts of boron remaining from the organoborane initiator (e.g., as oxidized by-products). In other words, the organoborane initiator includes boron atoms. After the reaction to form the poly(meth)acrylate, some of the boron atoms may remain in the poly(meth)acrylate. As just one example, the presence of boron atoms can differentiate the poly(meth)acrylate formed in the presence of the organoborane initiator from another poly(meth)acrylate formed using different initiation mechanisms or different initiators. In various embodiments, the amount of boron atoms in the poly(meth)acrylate can be from 10 to 10,000,000, from 10 to 1,000,000, from 10 to 100,000, from 100 to 10,000, from 100 to 5,000, from 500 to 5,000, or from 500 to 2,000, parts by weight per million parts by weight (ppm) of at least the (meth)acrylate or the poly(meth)acrylate. In alternative embodiments, all values and ranges of values between the aforementioned values are expressly contemplated herein.

em que cada um de R1 - R3 tem, independentemente, de 1 a 20 átomos de carbono e em que cada um de R1 - R3 compreende, independentemente, um grupo hidrocarboneto alifático e um grupo hidrocarboneto aromático. Os grupos de hidrocarbonetos alifáticos e/ou aromáticos podem ser lineares, ramificados e/ou cíclicos. Exemplos apropriados do organoborano incluem, mas não são limitados a, tri- metilborano, tri-etilborano, tri-n-butilborano, tri-n-octilborano, tri-sec- butilborano, tri-dodecilborano, fenildietilborano, e combinações dos mesmos. Em uma modalidade, o organoborano inclui tri-n-butilborano.[0023] The organoborane initiator may be any organoborane compound known in the art capable of generating free radicals. In various embodiments, the organoborane initiator includes trifunctional boranes that include the general structure:

wherein each of R1 - R3 independently has from 1 to 20 carbon atoms and wherein each of R1 - R3 independently comprises an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic and/or aromatic hydrocarbon groups may be linear, branched and/or cyclic. Suitable examples of organoborane include, but are not limited to, trimethylborane, triethylborane, tri-n-butylborane, tri-n-octylborane, tri-sec-butylborane, tri-dodecylborane, phenyldiethylborane, and combinations thereof. In one embodiment, the organoborane includes tri-n-butylborane.

em que B representa boro. Adicionalmente, cada um de R4, R5, e R6 é tipicamente selecionado independentemente do grupo de um átomo de hidrogênio, um grupo cicloalquila, um grupo alquila linear ou ramificado com 1 a 12 átomos de carbono em uma espinha dorsal, um grupo alquilarila, um grupo organossilano, um grupo organossiloxano, um grupo alquileno capaz de funcionar como uma ponte covalente para o boro, um grupo organossiloxano divalente capaz de funcionar como uma ponte covalente para o boro, e homólogos substituídos por halogêneo dos mesmos, de modo que pelo menos um de R4, R5, e R6 inclui um ou mais átomos de silício e é de forma covalente ligado ao boro. Adicionalmente, cada um de R7, R8, e R9 tipicamente produz um composto amina ou um composto poliamina capaz de complexar o boro. Dois ou mais de R4, R5, e R6 e dois ou mais de R7, R8, e R9 tipicamente se combinam para formar estruturas heterocíclicas, desde que uma soma do número de átomos de R4, R5, R6, R7, R8, e R9 não exceda 11.[0024] The organoborane initiator can be derived from the decomplexation of an air-stable complex of an organoborane compound and an organonitrogen compound. In one embodiment, the organoborane initiator is further defined as an organoborane-organonitrogen complex. Suitable organoborane initiators include, but are not limited to, organoborane-amine complexes, organoborane-azole complexes, organoborane-amidine complexes, organoborane-heterocyclic nitrogen complexes, amido-organoborane complexes, and combinations thereof. In one embodiment, the organoborane-amine complex is or includes a trialkylborane-amine complex. In one embodiment, the organoborane initiator is further defined as an organoborane-amine complex. A typical organoborane-amine complex includes a complex formed between an organoborane and an appropriate amine that makes the organoborane-amine complex stable under ambient conditions. Any organoborane-amine complex known in the art can be used. Typically, the organoborane-amine complex is capable of initiating polymerization or cross-linking of the curable organic compound by introducing an amine-reactive compound, and/or by heating. That is, the organoborane-amine complex can be destabilized at room temperature through exposure to appropriate amine-reactive compounds. Heat can be applied if needed or desired. The organoborane-amine complex typically has the formula:

where B represents boron. Additionally, each of R4, R5, and R6 is typically independently selected from the group of a hydrogen atom, a cycloalkyl group, a linear or branched alkyl group with 1 to 12 carbon atoms in a backbone, an alkylaryl group, a organosilane group, an organosiloxane group, an alkylene group capable of functioning as a covalent bridge to boron, a divalent organosiloxane group capable of functioning as a covalent bridge to boron, and halogen-substituted homologues thereof, so that at least one of R4 , R5 , and R6 includes one or more silicon atoms and is covalently bonded to boron. Additionally, each of R7, R8, and R9 typically produces an amine compound or a polyamine compound capable of complexing boron. Two or more of R4, R5, and R6 and two or more of R7, R8, and R9 typically combine to form heterocyclic structures, provided that a sum of the number of atoms of R4, R5, R6, R7, R8, and R9 do not exceed 11.

[0025] Additionally, any amine known in the art can be used to form the organoborane-amine complex. Typically, the amine includes at least one of an alkyl group, an alkoxy group, an imidazole group, an amidine group, an ureido group, and combinations thereof. Particularly suitable amines include, but are not limited to, 1,3-propane diamine, 1,6-hexanediamine, methoxypropylamine, pyridine, isophorone diamine and combinations thereof.

[0026] The organoborane initiator can be used in any amount to form the poly(meth)acrylate. Typically, the organoborane initiator is used in an amount equivalent to from 0.01 to 95, more typically from 0.1 to 80, even more typically from 0.1 to 30, even more typically from 1 to 20, and most typically from 1 to 15 parts by weight per 100 parts by weight of the poly(meth)acrylate. Organoborane initiator amounts typically depend on the molecular weight and functionality of the organoborane initiator and the presence of other components such as fillers. Organoborane initiator amounts typically depend on the molecular weight and functionality of the organoborane initiator and the presence of other components such as fillers. In various embodiments, the amount used is based on the percentage of boron in the reaction mixture, calculated by the weight of active ingredients/components (eg acrylic monomers).

[0027] In addition to the organoborane initiator, a reactive compound such as a decomplexer can also be used or can be omitted (if the decomplexer is omitted, heat is used to initiate the reaction). For example, an organoborane-organonitrogen complex (acting as the organoborane initiator) can interact with a nitrogen-reactive compound to initiate polymerization or cross-linking of the at least one acrylate. This allows at least one (meth)acrylate to polymerize at low temperatures and with reduced reaction times. Typically this occurs when the nitrogen-reactive compound is mixed with the organoborane-organonitrogen complex and exposed to an oxygenated environment at temperatures below an organoborane-organonitrogen complex dissociation temperature, including room temperature and below. The amine-reactive nitrogen-reactive compound may be or include any nitrogen-reactive compound known in the art and may be delivered as a gas, liquid, or solid. In one embodiment, the nitrogen-reactive compound includes free radical polymerizable groups or other functional groups such as a hydrolysable group, and may be monomeric, dimeric, oligomeric, or polymeric. In various embodiments, the organoborane-amine complex includes a trialkylborane-amine complex. In other embodiments, the amine-reactive compound is chosen from acids, anhydrides, and combinations thereof.

[0028] In various embodiments, the nitrogen-reactive compound is chosen from the group of an acid, an anhydride, and combinations thereof. In another embodiment, the nitrogen-reactive compound includes nitrogen-reactive groups, such as amine-reactive groups. It is contemplated that the nitrogen-reactive groups may be derived from the organoborane-organonitrogen complex and/or any additives present. The nitrogen-reactive compound can be selected from the group of Lewis acids, carboxylic acids, carboxylic acid derivatives, carboxylic acid salts, isocyanates, aldehydes, epoxides, acid chlorides, sulfonyl chlorides, iodonium salts, anhydrides, and combinations. of the same. In one embodiment, the amine-reactive compound is selected from the group of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, methyldiphenyl diisocyanate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxymethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, methacrylic anhydride, undecylenic acid, citraconic anhydride, polyacrylic acid, polymethacrylic acid, and combinations thereof. In yet another embodiment, the nitrogen-reactive compound is selected from the group of oleic acid, undecylenic acid, polymethacrylic acid, stearic acid, citric acid, levulinic acid, and 2-carboxyethyl acrylate, and combinations thereof. In another embodiment, the nitrogen-reactive compound may include, but is not limited to, acetic acid, acrylic acid, methacrylic acid, methacrylic anhydride, undecylenic acid, oleic acid, an isophorone diisocyanate monomer or oligomer, a monomer, hexamethylene diisocyanate oligomer or polymer, a toluene diisocyanate monomer, oligomer or polymer, methyldiphenyl diisocyanate monomer, oligomer or polymer, methacryloyl isocyanate, 2-(methacryloyloxy)ethyl acetoacetate, undecylenic aldehyde , dodecyl succinic anhydride, compounds capable of generating nitrogen-reactive groups when exposed to ultraviolet radiation, such as photoacid generators and iodonium salts, including counter-ions [SbF6]. With these ultraviolet photoacid generators, a photosensitizing compound such as isopropylthioxanthone can be included.

[0029] In various embodiments, the decomplexer includes at least one free radically polymerizable group and at least one nitrogen-reactive group in the same molecule. Examples of usable decomplexers include the following: (A)a-Y-(B)b wherein "A" is a group that is capable of forming a covalent bond with an acrylate, "B" is a group that is capable of forming a bond covalent with a nitrogen moiety (eg amine) of the organoborane-organonitrogen complex, "Y" is a polyvalent organic linking group; “a” represents the number of free radically polymerizable groups, and “b” represents the number of nitrogen-reactive groups.

[0030] The “A” group may include free radically polymerizable groups such as alkene groups. The alkene group may be unsubstituted or substituted or part of a cyclic ring structure. Substituted alkenes include, for example, those alkenes having substitution of the alkyl aryl group. Typical alkenes are those that have terminal unsubstituted double bonds, such as allyl groups. Other alkenes are styrene and acrylics.

[0031] The “B” group may include an isocyanate group. Typically, the value of each “a” and “b” is at least one. Preferably, the sum of "a" and "b" is less than or equal to six, more preferably less than or equal to four, most preferably two.

[0032] The “Y” group can include a variety of different chemical structures depending on the reagents used to prepare the decomplexer. The decomplexer may include the reaction product of a hydroxyl compound containing a free radically polymerizable group and a polyisocyanate.

[0033] The nitrogen-reactive decomplexer/compound may be used in an amount equivalent to from 0.1 to 95, more typically from 0.1 to 90, and most typically from 1 to 20, parts by weight per 100 parts by weight. weight of the poly(meth)acrylate. The amount of the nitrogen-reactive compound may depend on the molecular weight and functionality of the nitrogen-reactive compound and the presence of other components such as fillers. In another embodiment, the nitrogen-reactive compound is typically used in an amount where a molar ratio of nitrogen-reactive groups to nitrogen groups in the poly(meth)acrylate is from 0.1 to 100, more typically from 0.5 to 50. , and most typically from 0.8 to 20.

[0034] In various embodiments, the poly(meth)acrylate, the at least one (meth)acrylate, the organoborane initiator, the decomplexer, etc. may each be independently, as described in US Patent No. 5,990,036, which is expressly incorporated herein in its entirety in various non-limiting embodiments.

[0035] The poly(meth)acrylate layer (16) is not limited to any particular dimension or thickness. In various embodiments, the poly(meth)acrylate layer (16) has a wet film thickness of 0.025 to 0.5, 0.050 to 0.5, 0.025 to 0.1, 0.025 to 0.05, 0.05 to 0.1, or 0.05 to 0.5 inch (with 1 inch equaling about 2.54 cm). In still several additional embodiments, the poly(meth)acrylate layer (16) has a wet film thickness of 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100 inches (again with 1 inch equals about 2.54 cm). In various non-limiting embodiments, all values and ranges of values between the aforementioned values are expressly contemplated herein. In various non-limiting embodiments, there is no maximum film thickness per se.

Epoxide layer (18):

[0036] Referring now to the epoxide layer (18), the epoxide layer (18) is arranged on and in direct contact with the poly(meth)acrylate layer (16). In other words, there is no intermediate layer or bonding layer disposed between the poly(meth)acrylate layer (16) and the epoxide layer (18). The epoxide layer (18) may include, consist essentially of, or consist of, an epoxide. The epoxide layer (18), and the epoxide itself, are typically formed from an epoxide composition. The epoxy layer (18) may alternatively be described as a "bonding layer" or "bonding coat" between the hydrolytically resistant layer (20) and the poly(meth)acrylate layer (16). In various embodiments, the epoxide layer (18) is used to prevent the hydrolytically resistant layer (20) from contacting the poly(meth)acrylate layer (16). For example, if a composition that is used to form the hydrolytically resistant layer (20) (which may include an isocyanate and a polyol) is poured into the poly(meth)acrylate layer (16), undesirable foaming can occur. Therefore, the epoxy layer (18) can be used to minimize or eliminate this foaming by minimizing or eliminating contact between the hydrolytically resistant layer (20) and the poly(meth)acrylate layer (16).

[0037] The epoxy composition may include an epoxy compound and a hardener. Alternatively, the epoxy composition can be formed from the reaction of an epoxy compound (such as an epoxy resin) and a hardener. The epoxy resin chosen from epoxy resins that are liquid and water insoluble, and that have low viscosity and poor water permeability. In various embodiments, the epoxy resin is a common glycidyl ether type epoxy resin including bisphenol A type, bisphenol AD type, novolac type, bisphenol F type, and brominated bisphenol A type, special epoxy resins such as glycidyl ester type epoxy resins, glycidyl amine, and heterocyclic epoxy resins, and various modified epoxy resins. In various embodiments, epoxy resins usable herein include liquids, solids, and mixtures thereof. For example, epoxy resins can also be described as polyepoxides, such as monomeric polyepoxides (e.g., bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, novolac-based epoxy resins, and tris - epoxy), higher molecular weight resins (e.g. bisphenol A diglycidyl ether advanced with bisphenol A) or polymerized unsaturated monoepoxides (e.g. glycidyl acrylates, glycidyl methacrylate, allyl glycidyl ether, etc.) for homopolymers or copolymers. In various embodiments, epoxy compounds include, on average, at least one pendant or terminal 1,2-epoxy group (i.e., vicinal epoxy group) per molecule. Solid epoxy resins that can be used can include or be based on Bisphenol A. For example, a suitable epoxy resin is Dow Chemical DER 664 UE bisphenol A diglycidyl ether solid epoxy.

[0038] Bisphenol A type epoxy resins can be produced by reaction between 2,2-bis(4-hydroxyphenyl) propane, i.e. bisphenol A and haloepoxides such as epichlorohydrin or beta-methylepichlorohydrin. Bisphenol AD type epoxy resins can be produced by reacting between 1,1-bis(4-hydroxyphenyl)ethane, i.e. bisphenol AD and haloepoxides such as epichlorohydrin or beta-methylepichlorohydrin. Bisphenol F type epoxy resins can be produced by reaction between bis(4-hydroxyphenyl)methane i.e. bisphenol F and haloepoxides such as epichlorohydrin or beta-methylepichlorohydrin.

[0039] A modifier resin can also be mixed with the epoxy resin and chosen from a coumarone-indene polymer resin, a dicyclopentadiene polymer resin, an acrylonitrile-modified polyvinyl chloride resin, an acrylonitrile-copolymer resin amino-terminated butadiene, and an epoxy-terminated polybutadiene resin.

[0040] The hardener is typically capable of crosslinking with epoxy groups in the epoxy resin. Any hardener, for example suitable for a 2K epoxy, can be used. Typical hardeners include polymeric amines (polyamines) and polymeric amides (polyamides) (including, for example, polyamidoamines), low molecular weight amines, and combinations thereof.

[0041] In various embodiments, an amine is chosen from among a cycloaliphatic polyamine, an aliphatic/aromatic polyamine, and an amine adduct. The amine may be a linear aliphatic polyamine, aromatic polyamine, acid anhydride, imidazole or an amine selected from a cycloaliphatic polyamine, an aliphatic/aromatic polyamine, and an amine adduct. In various embodiments, the amine is isophorone diamine and/or m-xylylene diamine. In additional embodiments, the amine adduct is an adduct of a polyamine with an epoxy resin or the like. More particularly, the amine adducts can include polyamines such as m-xylylene diamine and isophorone diamine, to which various epoxy resins can be added, such as the bisphenol A epoxy resins. Epoxy resins that can form adducts with the polyamines are as described above. .

[0042] In various embodiments, the amine includes a polyetheramine-epoxy adduct, i.e., a reaction product of a stoichiometric excess of an amine prepolymer with an epoxy resin. The amine can be any amine prepolymer that has at least two amine groups in order to allow cross-linking to take place. The amine prepolymer may include primary and/or secondary amine groups, and typically includes primary amine groups. Suitable amine prepolymers include polyether diamines and polyether triamines and mixtures thereof. Polyether triamine is preferred in one embodiment. Polyether amines can be linear, branched or a mixture. Branched polyether amines are preferred in one embodiment. Any molecular weight polyetheramine can be used, with molecular weights in the range of 200-6000 or above being appropriate. Molecular weights may be above 1000, or more preferably above 3000. Molecular weights of 3000 or 5000 are preferred in various embodiments. Suitable commercially available polyetheramines include those sold by Huntsman under the tradename Jeffamine. Suitable polyether diamines include Jeffamines in the D, ED and DR series. These include Jeffamine D-230, D-400, D-2000, D-4000, HK-511, ED-600, ED-900, ED-2003, EDR-148, and EDR-176. Suitable polyether triamines include Jeffamines in the T series. These include Jeffamine T-403, T-3000, and T-5000. Polyether triamines are preferred in several embodiments, and a polyether triamine of molecular weight of about 5000 (e.g. Jeffamine T-5000) is more preferred in another embodiment. Equivalents of any of the above may also be used in partial or total replacement.

[0043] In further embodiments, the epoxy composition includes 5 to 30 parts by weight of the epoxy compound, 0 to 35 parts by weight of the modifier resin, and a remainder of the amine curing agent, per 100 parts by weight of the composition.

[0044] The epoxide composition may also include one or more curing accelerators (catalysts). The curing accelerator typically works by catalyzing the reaction of the epoxy resin and the amine (or hardener). The curing accelerator may include a tertiary amine, such as 2,4,6-tris(dimethylamino-methyl)phenol, available from Air Products under the name Ancamine K54. Other amines are described in US Patent No. 4,659,779 which is expressly incorporated herein by reference in its entirety in various non-limiting embodiments.

em que n é de 5 a 75.[0045] In various embodiments, the reaction of the epoxy resin and the amine is as follows:

where n is from 5 to 75.

[0046] The epoxy layer (18) is not limited to any particular dimension or thickness. In various embodiments, the epoxy layer (18) has a wet film thickness of 0.010 to 0.5, 0.025 to 0.5, 0.050 to 0.5, 0.025 to 0.1, 0.025 to 0.0 05, 0.05 to 0.1, or 0.05 to 0.5 inch (with 1 inch equaling about 2.54 cm). In various non-limiting embodiments, all values and ranges of values between the aforementioned values are expressly contemplated herein.

Hydrolytically resistant layer (20):

[0047] The hydrolytically resistant layer (20) is arranged on and in direct contact with the epoxide layer (18). In other words, there is no intermediate layer or bonding layer disposed between the hydrolytically resistant layer (20) and the epoxide layer (18). The hydrolytically resistant layer (20) may include, consist essentially of, or consist of, a hydrolytically resistant layer. The hydrolytically resistant elastomer may be a polyurethane elastomer. The polyurethane elastomer may be formed from a polyurethane elastomer composition. This composition may include the reaction product of an isocyanate component and an isocyanate-reactive component.

[0048] A hydrolytically resistant material, as defined herein, such as hydrolytically resistant elastomer, is a material (or elastomer) that is resistant to degradation in water.

[0049] The isocyanate component may be, include, consist essentially of, or consist of, any isocyanate known in the art, for example, aliphatic isocyanates, aromatic isocyanates, polymeric isocyanates, or combinations thereof. The isocyanate component may be, include, consist essentially of, or consist of more than one different isocyanate, for example, polymeric diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate. In various embodiments, the isocyanate is chosen from among diphenylmethane diisocyanates (MDIs), polymeric diphenylmethane diisocyanates (pMDIs), toluene diisocyanates (TDIs), hexamethylene diisocyanates (HDIs), isophorone (IPDIs), and combinations thereof.

[0050] In various embodiments, the isocyanate component typically includes, but is not limited to, isocyanates, diisocyanates, polyisocyanates, and combinations thereof. In one embodiment, the isocyanate component includes a non-functional isocyanate. In this embodiment, n is a number typically from 2 to 5, more typically from 2 to 4, even more typically from 2 to 3, and more typically about 2. It should be understood that n can be an integer or can have intermediate values of 2 to 5. The isocyanate component typically includes an isocyanate selected from the group of aromatic isocyanates, aliphatic isocyanates and combinations thereof. In another embodiment, the isocyanate component includes an aliphatic isocyanate such as hexamethylene diisocyanate (HDI), dicyclohexyl-methyl-diisocyanate (H12MDI), isophorone diisocyanate, and combinations thereof. If the isocyanate component includes an aliphatic isocyanate, the isocyanate component may also include a modified multivalent aliphatic isocyanate, i.e. a product that is obtained through chemical reactions of aliphatic diisocyanates and/or aliphatic polyisocyanates. Examples include, but are not limited to, ureas, biurets, allophanates, carbodiimides, uretonimines, isocyanurates, urethane groups, dimers, trimers and combinations thereof. The isocyanate component may also include, but is not limited to, modified diisocyanates employed individually or in reaction products with polyoxyalkylene glycols, diethylene glycols, dipropylene glycols, polyoxyethylene glycols, polyoxypropylene glycols, polyoxypropylenepolyoxyethylene glycols, polyesters, polycaprolactones, and combinations thereof. .

[0051] Alternatively, the isocyanate component may include an aromatic isocyanate. If the isocyanate component includes an aromatic isocyanate, the aromatic isocyanate typically corresponds to the formula R'(NCO)z where R' is aromatic and z is an integer corresponding to the valence of R'. Typically, z is at least two. Suitable examples of aromatic isocyanates include, but are not limited to, tetramethylxylylene diisocyanate (TMXDI), 1,4-diisocyanatobenzene, 1,3-diisocyanate-o-xylene, 1,3-diisocyanate- p-xylene, 1,3-diisocyanate-m-xylene, 2,4-diisocyanato-1-chlorobenzene, 2,4-diisocyanato-1-nitro-benzene, 2,5-diisocyanato- 1-nitrobenzene, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4-diisocyanate mixtures and 2,6-toluene, 1,5-naphthalene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diisocyanate -diphenylmethane, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, tri- isocyanates such as 4,4',4”-triphenylmethane triisocyanate, polymethylene polyphenylene polyisocyanate and 2,4,6-toluene triisocyanate, tetraisocyanates such as 4,4'-dimethyl-2 tetraisocyanate, 2'-5,5'-diphenylmethane, toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, poly -polymethylene polyphenylene isocyanate, corresponding isomeric mixtures thereof and combinations thereof. Alternatively, the aromatic isocyanate may include a triisocyanate product of m-TMXDI and 1,1,1-trimethylolpropane, a reaction product of toluene diisocyanate and 1,1,1-trimethiolpropane, and combinations thereof. In one embodiment, the isocyanate component includes a diisocyanate selected from the group of diphenyl methylene diisocyanates, toluene diisocyanates, hexamethylene diisocyanates, H12MDIs, and combinations thereof.

[0052] The isocyanate component may be an isocyanate prepolymer. The isocyanate prepolymer may be a reaction product of an isocyanate and a polyol and/or a polyamine. The isocyanate used in the prepolymer can be any isocyanate as described above.

[0053] The polyol used to form the prepolymer can be one or more polyols described herein typically having a number average molecular weight (Mn) of 400 g/mol or greater, with (Mn) measured by conventional techniques such as GPC . Polyols suitable for use in the prepolymer are typically selected from the group of conventional polyols such as polyether polyols, polyester polyols, ether/polyester polyols and combinations thereof.

[0054] The one or more polyols can each be independently polyether polyols, polyester polyols, polyether/ester polyols, and combinations thereof. The one or more polyols may independently have a number average molecular weight of from about 400 to about 15,000, alternatively from about 450 to about 7,000, and alternatively from about 600 to about 5,000 g/mol. In another embodiment, each of the one or more polyols independently has a hydroxyl number of from about 20 to about 1000, alternatively from about 30 to about 800, alternatively from about 40 to about 600, alternatively from about 40 to about 600. 50 to about 500, alternatively from about 55 to about 450, alternatively from about 60 to about 400, alternatively from about 65 to about 300, mg KOH/g.

[0055] In various embodiments, the polyol is chosen from conventional polyols, including, but not limited to, biopolyols such as soybean oil, castor oil, soybean protein, rapeseed oil, etc., derivatives thereof, and combinations thereof. Suitable polyether polyols include, but are not limited to, products obtained by polymerizing a cyclic oxide, for example ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO) or tetrahydrofuran in the presence of initiators. multifunctional. Suitable starter compounds contain a plurality of active hydrogen atoms, and include water, butanediol, ethylene glycol, propylene glycol (PG), diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene diamine, diethyl toluene diamine, phenyl diamine, diphenylmethane diamine, ethylene diamine, cyclohexane diamine, cyclohexane dimethanol, resorcinol, bisphenol A, glycerol, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, and combinations thereof.

[0056] Other suitable polyether polyol copolymers include polyether diols and triols, such as polyoxypropylene diols and triols and poly(oxyethylene-oxypropylene) diols and triols obtained by the simultaneous or sequential addition of ethylene and propylene oxides to di- or trifunctional initiators. Copolymers having oxyethylene contents of from about 5 to about 90% by weight, based on the weight of the polyol component, of which the polyols may be block copolymers, random/block copolymers or random copolymers, can also be used. Still other suitable polyether polyols include polytetramethylene glycols obtained by polymerizing tetrahydrofuran.

[0057] Suitable polyester polyols include, but are not limited to, aromatic polyester polyols, hydroxyl terminated reaction products of polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1 ,6-hexanediol, cyclohexane dimethanol, glycerol, trimethylolpropane, pentaerythritol or polyether polyols or mixtures of such polyhydric alcohols, and polycarboxylic acids, especially dicarboxylic acids or ester forming derivatives thereof, for example succinic, glutaric and adipic acids or their dimethyl esters of sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride or dimethyl terephthalate or mixtures thereof. Polyester polyols obtained by polymerizing lactones, for example caprolactone, together with a polyol, or hydroxy carboxylic acids, for example hydroxy caproic acid, can also be used.

[0058] Suitable Polyesteramide Polyols can be obtained by including aminoalcohols such as ethanolamine in polyesterification blends. Suitable polythioether polyols include products obtained by condensation of thiodiglycol alone or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, aminoalcohols or aminocarboxylic acids. Suitable polycarbonate polyols include products obtained by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol or tetraethylene glycol with diaryl carbonates, e.g. diphenyl carbonates, or with phosgene . Suitable polyacetal polyols include those prepared by reacting glycols such as diethylene glycol, triethylene glycol or hexanediol with formaldehyde. Other suitable polyacetal polyols can also be prepared by polymerizing cyclic acetals. Suitable polyolefin polyols include hydroxy-terminated butadiene homo- and copolymers and polysiloxane polyols. Suitable polyols include polydimethylsiloxane diols and triols.

[0059] Specific isocyanates that can be included in the isocyanate component to prepare the isocyanate prepolymer include, but are not limited to, toluene diisocyanate; 4,4'-diphenylmethane diisocyanate; m-phenylene diisocyanate; 1,5-naphthalene diisocyanate; 4-chloro-1; 3-phenylene diisocyanate; tetramethylene diisocyanate; hexamethylene diisocyanate; 1,4-dicyclohexyl diisocyanate; 1,4-cyclohexyl diisocyanate, 2,4,6-toluylene triisocyanate, 1,3-diisopropylphenylene-2,4-diisocyanate; 1-methyl-3,5-diethylphenylene-2,4-diisocyanate; 1,3,5-triethylphenylene-2,4-diisocyanate; 1,3,5-triisopropyl-phenylene-2,4-diisocyanate; 3,3'-diethyl-bisphenyl-4,4'-diisocyanate; 3,5,3',5'-tetraethyl-diphenylmethane-4,4'-diisocyanate; 3,5,3',5'-tetraisopropyldiphenylmethane-4,4'-diisocyanate; 1-ethyl-4-ethoxy-phenyl-2,5-diisocyanate; 1,3,5-triethylbenzene-2,4,6-triisocyanate; 1-ethyl-3,5-diisopropyl benzene-2,4,6-triisocyanate and 1,3,5-triisopropyl benzene-2,4,6-triisocyanate. Other suitable polyurethane elastomer compositions can also be prepared from aromatic diisocyanates or isocyanates having one or two aryl, alkyl, aralkyl or alkoxy substituents wherein at least one of these substituents has at least two carbon atoms.

[0060] The isocyanate component typically has an NCO content of 3 to 50, alternatively 3 to 33, alternatively 18 to 30 percent by weight when tested in accordance with DIN EN ISO 11909, and a viscosity at 25°C from 5 to 2000, alternatively from 100 to 1000, alternatively from 150 to 250, alternatively from 180 to 220, mPa^s when tested according to DIN EN ISO 3219.

[0061] In various embodiments, the isocyanate component is, includes, essentially consists of, or consists of monomeric and polymeric isocyanate. For example, in one embodiment, the isocyanate component includes polymeric diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, and has an NCO content of from about 30 to 33.5 percent by weight. Alternatively, in another embodiment, the isocyanate component includes polymeric diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, and has an NCO content of about 31.3 weight percent.

[0062] The isocyanate component is typically reacted to form the hydrolytically resistant polyurethane elastomer composition in an amount comprised between 10 to 90, alternatively 20 to 75, alternatively 30 to 60 percent by weight, based on total weight of all components used to form the polyurethane elastomer composition. The amount of the reacted aliphatic isocyanate component to form the hydrolytically resistant polyurethane elastomer composition may vary outside the above ranges, but is typically integer and fractional values within these ranges. Additionally, it should be appreciated that more than one isocyanate may be included in the isocyanate component, in which case the total amount of all isocyanates included is within the above ranges.

[0063] Referring now to the isocyanate-reactive component, this component may be, include, consist essentially of, or consist of, a polydiene polyol.

[0064] The polydiene polyol comprises polymerized diene units. For purposes of the present invention, the term "diene units" is used to describe units within a polymer that have been formed from a diene or diolefin, i.e., a hydrocarbon with two carbon-carbon double bonds. Examples of dienes that can be used from the polydiene include, but are not limited to, 1,2-propadiene, isoprene, and 1,3-butadiene.

[0065] In one embodiment, the polydiene polyol is a polybutadiene polyol, i.e. it is formed from 1,3-butadiene and therefore comprises butadiene units. Of course, 1,3-butadiene can polymerize to form 1,4-cis units, 1,4-trans units and 1,2-vinyl units. The polybutadiene polyol may include not less than 10, alternatively not less than 15, alternatively not less than 20, alternatively not less than 25, alternatively not less than 30, alternatively not less than 35, alternatively not less than than 40, alternatively not less than 45, alternatively not less than 50, alternatively not less than 55, alternatively not less than 60, alternatively not less than 65, weight percent 1,2-vinyl units with based on the total weight of the polybutadiene polyol. The structure of the polybutadiene polyol is believed to impart hydrolytic stability to the hydrolytically resistant layer (20). It is also believed that the structure of the polybutadiene polyol imparts hydrophobicity to the hydrolytically resistant layer (20).

[0066] The polydiene polyol typically has an average hydroxyl functionality of not greater than about 3, alternatively from about 2 to about 3, alternatively from about 2. The polybutadiene polyol may include an average hydroxyl functionality of no greater than 3, alternatively not greater than 2.7, alternatively not greater than 2.6, alternatively not greater than 2.5, alternatively greater than 2.4, alternatively not greater than 2.3, alternatively not greater than than 2.1, alternatively not greater than 2.0. In one embodiment, the polydiene polyol is terminated with hydroxyl groups. In another embodiment, the polydiene polyol is terminated at both ends with hydroxyl groups. In another embodiment, the polydiene polyol is a hydroxy-terminated polybutadiene, i.e., it is a linear polybutadiene having two primary hydroxy functional groups. In another embodiment, the hydroxy-terminated polybutadiene is terminated at each end with a hydroxy functional group.

[0067] The polydiene polyol typically has a number average molecular weight of from about 1000 to less than about 3000, alternatively from about 1000 to less than about 2200, alternatively from 1100 to 2000, alternatively from 1200 to 1800, alternatively from 1300 to 1700, alternatively from 1400 to 1600, g/mol, and a viscosity at 30°C of from 0.5 to 6.0, alternatively from 0.5 to 2.5, alternatively from 0.7 to 2.3, alternatively from 0.8 to 2.1, alternatively from 0.9 to 1.9, Pa^s, when tested in accordance with DIN EN ISO 3219, modified for a viscosity measurement at 30°C.

[0068] Suitable polydiene polyols are commercially available from TOTAL of Houston, TX under the trade names Poli bd® or Krasol®.

[0069] In an exemplary embodiment, the polydiene polyol is a hydroxyl-terminated polybutadiene having about 20 weight percent 1,2-vinyl units, a molecular weight of about 1200 to 1350 g/mol, and a viscosity at 30°C from about 0.9 to 1.9 Pa2s. In another exemplary embodiment, the polydiene polyol is a hydroxyl terminated polybutadiene having about 20 weight percent 1,2-vinyl units, a molecular weight of about 1200 g/mol, and a viscosity at 30°C of about 1.4 Pa 2 s. In yet another exemplary embodiment, the polydiene polyol is a hydroxyl terminated polybutadiene having about 20 weight percent 1,2-vinyl units, a molecular weight of about 1350 g/mol, and a viscosity at 30°C. of about 1.4 Pa 2 s. It is believed that due to the concentration of 1,2-vinyl units, i.e., olefinic double bonds and low molecular weight, the hydroxy-terminated polybutadiene of this embodiment is a liquid at room temperature. The liquid is typically clear and white like water. The liquid form facilitates the formation of a consistent and uniform polyurethane elastomeric composition coating over subsea structures. Additionally, the polybutadiene polyol imparts hydrolytic stability, low moisture permeability and/or low temperature flexibility to the polyurethane elastomeric composition. Alternatively, a polydiene polyol which is a hydroxy terminated polybutadiene having about 20 weight percent 1,2-vinyl units, a molecular weight of about 2800 g/mol, and a viscosity at 30°C of about 5 Pa^s can be used.

[0070] The polydiene polyol is typically present in the isocyanate-reactive component in an amount greater than 0 and less than 95 parts by weight, based on 100 parts by weight of said isocyanate-reactive component, alternatively from 10 to 95 , alternatively from 30 to 90, alternatively from 50 to 90, alternatively from 60 to 90, alternatively from 60 to 80, parts by weight, based on 100 parts by weight of the isocyanate-reactive component. The amount of polydiene polyol may vary outside the above ranges, but may be either integer or fractional values within these ranges. Additionally, it should be understood that more than one polydiene polyol may be included in the isocyanate-reactive component, in which case the total amount of all polydiene polyols included is within the above ranges.

[0071] In addition to the polydiene polyol, the isocyanate-reactive component may also include one or more additional polyols. If included, the supplementary polyol is typically selected from the group of conventional polyols that are not polydiene polyols, such as polyether polyols, polyester polyols, ether/polyester polyols and combinations thereof. In one embodiment, the supplemental polyol has a water content below 0.05% by weight, based on the total weight of the polyol. In further embodiments, the supplemental polyol has a total sodium (Na) and potassium (K) content of less than about 15, alternatively less than about 10, alternatively less than about 5 ppm. In one embodiment, the isocyanate-reactive component may also comprise a polyether polyol having a higher average hydroxy functionality, for example, greater than about 3. In another embodiment, the polyether polyol and the polydiene polyol together have an average functionality of hydroxy not greater than about 3, alternatively from about 2 to about 3, alternatively from about 2. The polyether polyol and polybutadiene polyol together may include an average hydroxy functionality of not greater than 3, alternatively not greater than 2.7, alternatively not greater than 2.6, alternatively not greater than 2.5, alternatively greater than 2.4, alternatively not greater than 2.3, alternatively not greater than 2.1, alternatively not greater than 1.9, alternatively not greater than 1.7.

[0072] Polyether polyols suitable for use as the supplementary polyol include, but are not limited to, products obtained by polymerization of a cyclic oxide, for example ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO ) or tetrahydrofuran in the presence of polyfunctional initiators. Suitable starter compounds contain a plurality of active hydrogen atoms, and include water, butanediol, ethylene glycol, propylene glycol (PG), diethylene glycol, triethylene glycol, dipropylene glycol, ethanolamine, diethanolamine, triethanolamine, toluene diamine, diethyl toluene diamine, phenyl diamine, diphenylmethane diamine, ethylene diamine, cyclohexane diamine, cyclohexane dimethanol, resorcinol, bisphenol A, glycerol, trimethylolpropane, 1,2,6-hexanetriol, pentaerythritol, and combinations thereof.

[0073] Other polyether polyols suitable for use as the supplemental polyol are polyether polyol copolymers that include polyether diols and triols, such as polyoxypropylene diols and triols and poly(oxyethylene-oxypropylene) diols and triols obtained by the simultaneous or sequential addition of oxides from ethylene and propylene to di- or trifunctional initiators. Copolymers having oxyethylene contents of from about 5 to about 90% by weight, based on the weight of the polyol component, of which the polyols may be block copolymers, random/block copolymers or random copolymers, can also be used. Still other suitable polyether polyols include polytetramethylene glycols obtained by polymerizing tetrahydrofuran.

[0074] Polyester polyols suitable for use as the supplemental polyol include, but are not limited to, aromatic polyester polyols, hydroxyl-terminated reaction products of polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,4 -butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexane dimethanol, glycerol, trimethylolpropane, pentaerythritol or polyether polyols or mixtures of such polyhydric alcohols, and polycarboxylic acids, especially dicarboxylic acids or ester-forming derivatives thereof, for example acids succinic, glutaric and adipic or their dimethyl esters of sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride or dimethyl terephthalate or mixtures thereof. Polyester polyols obtained by polymerizing lactones, for example caprolactone, together with a polyol, or hydroxy carboxylic acids, for example hydroxy caproic acid, can also be used.

[0075] Polyesteramide polyols suitable for use as the supplemental polyol can be obtained by including aminoalcohols such as ethanolamine in polyesterification blends. Polythioether polyols suitable for use as the supplemental polyol include products obtained by condensation of thiodiglycol alone or with other glycols, alkylene oxides, dicarboxylic acids, formaldehyde, aminoalcohols or aminocarboxylic acids. Polycarbonate polyols suitable for use as the supplemental polyol include products obtained by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol or tetraethylene glycol with diaryl carbonates, for example carbonates diphenyl, or with phosgene. Polyacetal polyols suitable for use as the supplemental polyol include those prepared by reacting glycols such as diethylene glycol, triethylene glycol or hexanediol with formaldehyde. Other polyacetal polyols suitable for use as the supplemental polyol can also be prepared by polymerizing cyclic acetals. Suitable polyolefin polyols for use as the supplemental polyol include homo- and copolymers of hydroxyl-terminated butadiene and polysiloxane polyols. Suitable polyols include polydimethylsiloxane diols and triols.

[0076] Other suitable supplementary polyols include, but are not limited to, biopolyols such as soybean oil, castor oil, soybean protein, rapeseed oil, etc., and derivatives and combinations thereof.

[0077] In addition, lower molecular weight hydroxyl functional compounds can also be used such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butane diol, glycerol, trimethylpropane, triethanolamine, pentaerythritol, sorbitol, and combinations thereof. The supplemental polyol may be included in the isocyanate-reactive component in an amount of 1 to 70, alternatively 5 to 50, alternatively 5 to 25 percent by weight, based on the total weight of all components included in the isocyanate-reactive component. . The amount of supplemental polyol may vary outside the above ranges, but may be either integer or fractional values within these ranges. Additionally, it should be understood that more than one supplemental polyol may be included in the isocyanate-reactive component, in which case the total amount of all supplementary polyol included is within the above ranges. Particularly suitable supplementary polyols are commercially available from BASF Corporation of Wyandotte, MI, under the tradename Pluracol®. In a preferred embodiment, the supplemental polyol is a polyether polyol available from BASF Corporation of Wyandotte, MI under the tradename Pluracol® 2010.

[0078] In another embodiment, the supplemental polyol has a number average molecular weight of from about 400 to about 15,000, alternatively from about 450 to about 7,000, and alternatively from about 600 to about 5,000 g/mol . In another embodiment, the supplemental polyol has a hydroxyl number from about 20 to about 1000, alternatively from about 30 to about 800, alternatively from about 40 to about 600, alternatively from about 50 to about 500 alternatively from about 55 to about 450, alternatively from about 60 to about 400, alternatively from about 65 to about 300, mg KOH/g. In yet another embodiment, the supplemental polyol has a nominal hydroxy functionality of from about 2 to about 4, alternatively from about 2.2 to about 3.7, and alternatively from about 2.5 to about 3.5 .

[0079] In addition to the polydiene polyol, the isocyanate-reactive component may also include one or more chain extenders and/or crosslinkers (hereinafter referred to collectively as chain extenders. The chain extender has at least two hydroxyl functional groups and a weight number average not greater than 400 g/mol. Specifically, the chain extender typically has a nominal functionality of not greater than 4, alternatively not greater than 3, alternatively not greater than 2.5, alternatively 1, 9 to 3.1, alternatively from 1.9 to 2.5, and a number average molecular weight from 50 to 400, alternatively from 60 to 300, alternatively from 62 to 220, alternatively from 70 to 220, alternatively from 75 to 195, alternatively about 192, alternatively about 134, alternatively about 76.

[0080] Non-limiting examples of such chain extenders include, but are not limited to, straight-chain glycols with 2 to 20 carbon atoms in the main chain, diols with an aromatic ring and up to 20 carbon atoms, and even triols. such as those shown below. Examples of suitable chain extenders for purposes of the present invention include propylene glycol, dipropylene glycol, tripropylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-butene-1,4-diol, thiodiethanol, butylene glycol, 1,4-bis(hydroxyethoxy)benzene, p-xylene glycol and hydrogenated products thereof, trimethylol, stearyl alcohol, N,N-diisopropanol aniline, 2- ethyl-1,3-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, and ethyl hydroxyacrylate. In one embodiment, the chain extender may comprise an alkylene glycol. In a specific embodiment, the alkylene glycol is selected from the group of propylene glycol, dipropylene glycol, tripropylene glycol, and combinations thereof. In another embodiment, the chain extender is dipropylene glycol. The chain extender is believed to impart even higher hydrolytic strength as well as increased strength, tear strength and hardness to the polyurethane elastomeric composition as a result of its low molecular weight and molecular structure, e.g. ether groups.

[0081] In one embodiment, the isocyanate-reactive component essentially consists of the chain extender comprising the polydiene polyol and an alkylene glycol. In this and additional embodiments, the chain extender may present in the isocyanate-reactive component in an amount greater than about 5, alternatively more than about 10, alternatively more than about 15, alternatively more than about 20 parts by weight, based on 100 parts by weight of all components included in the isocyanate-reactive component. In other embodiments, the chain extender may be present in the isocyanate-reactive component in an amount of less than 30, alternatively less than about 25, alternatively less than about 20 parts by weight, based on 100 parts by weight. weight of all components included in the isocyanate-reactive component. In another embodiment, the isocyanate-reactive component consists essentially of the chain extender which comprises an alkylene glycol, the polydiene polyol, and an additional polyester polyol. The string extender amount may vary outside the above ranges, but may be integer and fractional values within these ranges. Additionally, it should be appreciated that more than one chain extender may be included in the isocyanate-reactive component, in which case the total amount of all chain extenders included is within the above ranges.

[0082] In addition to the polydiene polyol, the isocyanate-reactive component may also include one or more amines. Any amine known in the art can be used. For example, the amine can be chosen from MDA, TDA, ethylene-, propylene-butylene-, pentane-, hexane-, octane-, decane-, dodecane-, tetradecane-, hexadecane-, octadecanediamines, Jeffamines-200, -400 , -2000, -5000, hindered secondary amines such as Unilink 4200, Curene 442, Polacure 740, Ethacure 300, Lonzacure M-CDEA, Polyaspartics, 4,9 Dioxadodecan-1,12-diamine, and combinations thereof. In other embodiments, the amine is chosen from Lupragen® API - N-(3-Aminopropyl)imidazole, Lupragen® DMI - 1,2-Dimethylimidazole, Lupragen® DMI - 1,2-Dimethylimidazole, Lupragen® N 100 - N,N -Dimethylcyclohexylamine, Lupragen® N 101 - Dimethylethanolamine, Lupragen® N 103 - N,N-Dimethylbenzylamine, Lupragen® N 104 - N-Ethylmorpholine, Lupragen® N 105 - N-Methylmorpholine, Lupragen® N 106 - 2,2' -Dimorpholinodiethylether, Lupragen® N 107 - Dimethylaminoethoxyethanol, Lupragen® N 201 - TEDA in DPG, Lupragen® N 202 - TEDA in BDO, Lupragen® N 203 - TEDA in MEG, Lupragen® N 204 - N,N'-Dimethylpiperazine, Lupragen ® N 205 - Bis(2-dimethylaminoethyl)ether, Lupragen® N 206 - Bis(2-dimethylaminoethyl)ether, Lupragen® N 301 - Pentamethyldiethylenetriamine, Lupragen® N 301 - Pentamethyldiethylenetriamine, Lupragen® N 400 - Trimethylaminoethylethanolamine, Lupragen® N 500 - Tetramethyl-1,6-hexanediamine, Lupragen® N 500 - Tetramethyl-1,6-hexanediamine, Lupragen® N 600 - S-Triazine, Lupragen® N 700 - 1,8-Diazabicyclo-5,4,0-undec ene-7, Lupragen® NMI - N-Methylimidazole, and combinations thereof.

[0083] The isocyanate-reactive component may also include one or more catalysts. The catalyst is typically present in the isocyanate-reactive component to catalyze the reaction between the isocyanate component and the isocyanate-reactive component. That is, isocyanate-reactive component typically includes a "polyurethane catalyst" that catalyzes the reaction between an isocyanate and a hydroxy functional group of the isocyanate-reactive group, including a hydroxy group of the polydiene polyol. It should be appreciated that the catalyst is not typically consumed in the exothermic reaction between the isocyanate and the polyol. More specifically, the catalyst typically participates but is not consumed in the exothermic reaction. The catalyst may include any suitable catalyst or mixtures of catalysts known in the art. Examples of suitable catalysts include, but are not limited to, gelling catalysts, for example, amine catalysts in dipropylene glycol; blowing catalysts, for example bis(dimethylaminoethyl)ether in dipropylene glycol; and metal catalysts, for example organo-tin compounds, organo-bismuth compounds, organo-lead compounds, etc.

[0084] This catalyst can be anyone in the art. In one embodiment, the isocyanate catalyst is an amine catalyst. In another embodiment, the isocyanate catalyst is an organometallic catalyst.

[0085] The isocyanate catalyst may be or include a tin catalyst. Suitable tin catalysts include, but are not limited to, tin(II) salts of organic carboxylic acids, for example, tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate and laurate. of tin (II). In one embodiment, the isocyanate catalyst is or includes dibutyl tin dilaurate, which is a dialkyltin(IV) salt of an organic carboxylic acid. Specific examples of non-limiting isocyanate catalysts are commercially available from Air Products and Chemicals, Inc. of Allentown, PA, under the trademark DABCO®. The isocyanate catalyst may also include other dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin maleate and dioctyltin diacetate.

[0086] Examples of other suitable, but not limiting, isocyanate catalysts include iron(II) chloride; zinc chloride; lead octoate; tris(dialkylaminoalkyl)-s-hexahydrotriazines including tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine; tetraalkylammonium hydroxides including tetramethylammonium hydroxide; alkali metal hydroxides including sodium hydroxide and potassium hydroxide; alkali metal alkoxides including sodium methoxide and potassium isopropoxide; and alkali metal salts of long chain fatty acids having from 10 to 20 carbon atoms and/or side OH groups.

[0087] Additional examples of other suitable, but not limiting, isocyanate catalysts include N,N,N-dimethylaminopropylhexahydrotriazine, potassium, potassium acetate, N,N,N-trimethyl isopropyl amine/formate, and combinations thereof. A specific example of a suitable trimerization catalyst is commercially available from Air Products and Chemicals, Inc. under the POLYCAT® trademark.

[0088] Still further examples of other suitable, but not limiting, isocyanate catalysts include dimethylaminoethanol, dimethylaminoethoxyethanol, triethylamine, N,N,N',N'-tetramethylethylenediamine, N,N-dimethylaminopropylamine, N,N,N',N ',N"-pentamethyldipropylenetriamine, tris(dimethylaminopropyl)amine, N,N-dimethylpiperazine, tetramethyliminobis(propylamine), dimethylbenzylamine, trimethylamine, triethanolamine, N,N-diethylethanolamine, N-methylpyrrolidone, N-methylmorpholine, N-ethylmorpholine , bis(2-dimethylamino-ethyl)ether, N,N-dimethylcyclohexylamine (DMCHA), N,N,N',N',N'-pentamethyldiethylenetriamine, 1,2-dimethylimidazole, 3-(dimethylamino)propylimidazole, and combinations thereof. In various embodiments, the isocyanate catalyst is commercially available from Air Products and Chemicals, Inc. under the POLYCAT® trademark. The isocyanate catalyst may include any combination of one or more of the aforementioned catalysts.

[0089] In still other embodiments, the catalyst is chosen from among DABCO TMR, DABCO TMR-2, DABCO HE, DABCO 8154, PC CAT DBU TA 1, PC CAT Q1, Polycat SA-1, Polycat SA-102, salted and /or combinations thereof.

[0090] In other embodiments, the catalyst is chosen from among dibutyl tin dilaurate, dibutyl tin oxide (e.g. as a liquid solution in C8-C10 phthalate), dibutyl tin dilauryl mercaptide, bis(2-ethyl- dibutyl tin hexylthioglycolate), dimethyl tin dilauryl mercaptide, dimethyl tin dineodecanoate, dimethyl tin dioleate, dimethyl tin bis(2-ethylhexylthioglycoate), dioctyl tin dilaurate, bis(2-ethylhexoate) of dibutyl tin, tin octoate, stannous oleate, dibutyl tin dimaleate, dioctyl tin dimaleate, dibutyl tin maleate, dibutyl tin mercaptopropionate, dibutyl tin bis(isodithioglycolate), dibutyl tin diacetate, mixture of dioctyl tin oxide, dioctyl tin oxide, dibutyl tin diisooctoate, dibutyl tin dineodecanoate, dibutyl tin carboxylate, dioctyl tin carboxylate, and combinations thereof.

[0091] The isocyanate catalyst can be used in various amounts. For example, in various embodiments, the isocyanate catalyst is used in an amount of 0.0001 to 10, 0.0001 to 5, 5 to 10, weight percent, based on a total weight percent of reactants. or isocyanate or any other value or range of values in between. Typically, an amount of catalyst used depends on the temperature of the process. For example, at 150°F (about 65.5°C), 0.0001% can be used, while at room temperature 0.001 to 10%, such as 5-10%, such as 0.001 to 1%, can be used. .

[0092] The isocyanate-reactive component may also include a "curing agent", i.e., a crosslinker that crosslinks the carbon-carbon double bonds of the polydiene polyol. Examples of curing agents include, but are not limited to, organic peroxides, sulfur, and sulfur-containing organic compounds. Non-limiting examples of organic peroxides include dicumyl peroxide and t-butylperoxy-isopropyl benzene. Non-limiting examples of sulfur-containing organic compounds include thiuram-based vulcanization promoters such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and dipentamethylenethiuram tetrasulfide (DPTT), 4,4'-dithiomorpholine.

[0093] The isocyanate-reactive component may also include an adhesion promoter. The adhesion promoter may be a silicon-containing adhesion promoter. Adhesion promoters are also commonly referred to in the art as coupling agents or binding agents. The adhesion promoter facilitates the bonding of the polyurethane elastomeric coating composition to a subsea structure.

[0094] The isocyanate-reactive component may also include a wetting agent. The wetting agent may be a surfactant. The wetting agent may include any suitable wetting agent or mixtures of wetting agents known in the art. The wetting agent is employed to increase surface area contact between the polyurethane elastomeric composition and the subsea structure.

[0095] The isocyanate-reactive component may also include various additional additives. Suitable additives include, but are not limited to, defoaming agents, processing additives, plasticizers, chain terminators, surfactants, flame retardants, antioxidants, water sequestrants, fumigated silicas, dyes or pigments, ultraviolet light stabilizers, fillers, thixotropic agents, silicones, amines, transition metals, and combinations thereof. The additive may be included in any amount as desired by those skilled in the art.

[0096] For example, a pigment additive allows the polyurethane elastomeric composition to be visually evaluated for thickness and integrity and can provide several marketing advantages.

[0097] The hydrolytically resistant layer (20) is not limited to any particular dimension or thickness. In various embodiments, the hydrolytically resistant layer (20) has a thickness of 0.010 to 12, 0.010 to 6, 0.010 to 1, 0.010 to 0.5, 0.025 to 0.5, 0.050 to 0.5, from 0.025 to 0.1, from 0.025 to 0.05, from 0.05 to 0.1, from 0.05 to 0.5, from 1 to 12, from 2 to 11, from 3 to 10, from 4 to 9, 5 to 7, 5 to 6, 3 to 6, or 6 to 12 inches (with 1 inch equal to about 2.54 cm) In various non-limiting embodiments, all values and ranges of values between the aforementioned values are expressly contemplated herein.

[0098] The polyurethane elastomer composition to form layer (20) can be supplied in a system that includes the isocyanate component and the isocyanate-reactive component. The system can be supplied in two or more discrete components, such as the isocyanate component and the isocyanate-reactive component (or resin), i.e., as a two-component (or 2K) system, which is further described below. It should be appreciated that reference to the isocyanate component and the isocyanate-reactive component, as used herein, is merely for purposes of establishing a reference point for the placement of the individual components of the system, and to establish a basis of parts by weight. As such, it should not be interpreted as limiting the present disclosure to just one 2K system. For example, individual system components can be kept distinct from one another.

[0099] The hydrolytically resistant layer (20) and corresponding composition is formed by the reaction of the isocyanate component and the isocyanate-reactive component. Once formed, the hydrolytically resistant layer (20) and/or polyurethane elastomer composition is chemically and physically stable over a range of temperatures and typically does not decompose or degrade when exposed to higher pressures and temperatures, for example, pressures and temperatures greater than the pressures and temperatures typically found at the Earth's surface. As an example, the hydrolytically resistant polyurethane elastomer composition is particularly applicable when the composition is used as a layer (20) for a subsea structure (26) and is exposed to cold seawater at freezing temperature or above, for example , about 2 to 5°C, particularly from about 4°C, and significant pressure and hot oil temperatures of up to 150°C, such as about 120 to 150°C, particularly from 130 to 140°C. The hydrolytically resistant polyurethane elastomer composition is generally viscous to solid nature, and depending on molecular weight.

[00100] The polyurethane elastomer composition and/or hydrolysis resistant layer (20) may exhibit excellent non-wetting in the presence of water, fresh water or sea water, as measured according to standard contact angle measurement methods known in the art. The hydrolytically resistant layer (20) may have a contact angle greater than 90° and may be categorized as hydrophobic. Additionally, the hydrolytically resistant layer (20) typically exhibits excellent hydrolytic resistance and will not lose strength and durability when exposed to water. The polyurethane elastomer composition can be cured/crosslinked to form the hydrolytically resistant layer (20) prior to disposing of the subsea structure (26) in the ocean.

[00101] The hydrolytically resistant layer (20) can also exhibit excellent underwater thermal stability for high temperature and pressure applications. The hydrolytically resistant layer (20) may be stable at temperatures greater than 100, such as 102°C. The thermal stability of the hydrolytically resistant layer (20) is typically determined by thermal gravimetric analysis (TGA).

Composite article formation method (10):

[00102] This description also provides a method of forming the composite article (10). The method includes the steps of providing the first layer (14), providing the at least one acrylate and the organoborane initiator, providing the epoxide composition, providing the polyurethane composition, arranging the at least one acrylate and the organoborane initiator in the first layer. (14), polymerizing the at least one acrylate in the presence of the organoborane initiator to form the poly(meth)acrylate layer (16) which includes a poly(meth)acrylate and which is disposed on and in direct contact with the first layer ( 14), arranging the epoxide composition on the poly(meth)acrylate layer (16), curing the epoxide composition to form the epoxide layer (18) that includes the epoxide and which is disposed on and in direct contact with the layer of poly(meth)acrylate (16), layering the hydrolytically resistant polyurethane composition on the epoxide layer (18), and curing the hydrolytically resistant polyurethane elastomer composition to form the hydrolytically resistant layer (20) which includes the polyurethane elastomer in the hydrolytically resistant and which is arranged on and in direct contact with the epoxide layer (18).

[00103] Any one or more of the aforementioned provisioning steps may be any known in the art. For example, any one or more of the compositions may be provided or provided in individual components and/or as combinations of one or more components. Any one or more of the disposing steps can be further defined as applying, spraying, pouring, laying, brushing or coating, etc. The components of any one or more of the compositions may be arranged with, or independently of, any one or more other components. In one embodiment, the step of providing the first layer (14) is further defined as the provision of the first layer (14) which is already disposed in a tube (12). In such an embodiment, the first layer (14) can be used "in-situ" to form the multilayer coating (28) directly on the tube (12). Alternatively, the step of providing the first layer (14) may be further defined as providing the first layer (14) independently of the tube (12). In other words, the first layer (14) can be supplied and used independently of the tube (12). In fact, the tube (12) is not necessary in the method at all. The first layer (14) may be provided and used to form any of the embodiments of the multilayer coating (28) and/or the composite article (10).

[00104] For example, the hydrolytically resistant polyurethane elastomer composition to form layer (20) can be formed by providing the isocyanate component, providing the isocyanate-reactive component, and reacting the isocyanate component and the isocyanate-reactive component. The method may further include heating the isocyanate component and the isocyanate-reactive component. Alternatively, the method may include the step of combining the isocyanate component and the isocyanate-reactive component to form a reaction mixture, and applying the reaction mixture to form layer (20). The method may include spraying the reaction mixture.

[00105] The isocyanate-reactive component does not need to be formed prior to the application step. For example, the isocyanate component and the isocyanate-reactive component can be combined to form the reaction mixture simultaneously with the disposing or application step. Alternatively, the isocyanate component and the isocyanate-reactive component can be combined prior to the application step.

[00106] The individual components of any of the above mentioned compositions can be contacted in a spray device. The spray device may include a hose and container compartments. The components can then be sprayed. The poly(meth)acrylate and/or epoxide may react completely after spraying. Components can be separated immediately before being contacted at a spray device nozzle. The components can then be sprayed together, for example, on the subsea structure (26). Spraying generally results in an even, complete, defect-free coat. For example, the layer is typically uniform and unbroken. The layer also typically has appropriate thickness and acceptable integrity. Spraying also typically results in a thinner, more consistent coat compared to other techniques. Spraying allows for a continuous manufacturing process. The spray temperature is typically selected by one skilled in the art.

Underwater structure:

[00107] The composite article (10) may be further defined as an adhesive patch, film, cover, film or multi-layer coating, etc., for example, as shown in Figure 2. In various embodiments, the composite article (10) is used as an adhesive patch on/inside a subsea structure (26) as a structure for use during offshore oil and gas exploration engagements, as shown, for example, in Figure 1.

[00108] This description describes a subsea structure (26) including a tube (12) having a length, a first layer (14) disposed on the tube (12) and including the low surface energy polymer, and a multilayer coating (28). ) disposed on and in direct contact with the first layer (14). Tube (12) is not limited in composition and may be or include metal, polymers or combinations thereof. The multilayer coating (28) includes the poly(meth)acrylate layer (16) disposed on and in direct contact with the first layer (14), the epoxy layer (18) disposed on and in direct contact with the (meth)acrylate (16), and the hydrolytically resistant layer (20) disposed on and in direct contact with the epoxide layer (18), wherein the multilayer coating (28) has a peel strength of at least 50 pli, (with 1 pound per linear inch corresponding to 0.1786 kg per linear cm) measured between the hydrolytically resistant layer (20) and the epoxide layer (18) using ASTM D6862. In one embodiment, the first layer (14) includes a first section and a second section, wherein the first section is spaced from the second section along the length of the tube (12) and the multilayer coating (28) is disposed between said first and second sections, for example, as shown in figure 2.

[00109] Non-limiting examples of suitable subsea structures (26) include pipes (12), flowlines, pipelines, distribution headers, pipe-end terminators, pipe-end distribution headers, risers, in-use splices field, other joints, pipe connectors, pipe pigs, bending stoppers, bending stiffeners or Christmas trees. A Christmas tree is a well-known type of structure in the field of offshore oil and gas exploration. It should be understood that other structures not described herein may also be suitable for the purposes of the present description. The subsea structure (26) may be a tube (12) having a diameter of from about 12 to about 18 inches in diameter (wherein a 12 inch diameter is about a 30.48 cm diameter, and in that a diameter of 18 inches is about a diameter of 45.72 centimeters). The diameter of a subsea tube structure (12) is not limited, and can range from a few inches (i.e., a few centimeters), in the case of a flowline, to several feet (several meters). The length of the tube (12) is also not limited. In various embodiments, a multilayer coating (28) is used on the subsea structure (26) wherein the multilayer coating (28) is, consists of, or essentially consists of the poly(meth)acrylate layer (16), the layer of epoxide (18), and the hydrolytically resistant layer (20). For example, the first layer (14) can be arranged on the tube (12) and the multi-layer coating (28) can be formed using the first layer (14) which is already arranged on the tube (12). Alternatively, the multilayer coating (28) can be formed using the first layer (14) when the first layer (14) is not arranged on the tube (12) such that the multilayer coating (28) can then be arranged on the tube (12).

[00110] In various embodiments, the multilayer coating (28) insulates a portion of the subsea structure (26). For example, the multi-layer coating (28) can form a partial or full outer skin with a thickness on the structure intended for subsea applications. The thickness of the multilayer coating (28) may be half an inch thick (about 1.27 cm thick). Alternatively, the thickness of the multi-layer coating (28) may be one foot thick (about 30.48 cm thick). In one embodiment, the thickness of the hydrolytically resistant layer (20) can be about four inches (about 10.16 cm). In another embodiment, the thickness of the hydrolytically resistant layer (20) can be about six inches (about 15.24 cm). In yet another embodiment, the thickness of the hydrolytically resistant layer 20 can be about nine inches (about 22.86 cm).

[00111] In addition, the multi-layer coating (28) can isolate petroleum fuels, such as oil and/or gas, that flow through the subsea structure (26). The multi-layer coating (28) can coat a large enough surface area of a subsea structure (26) so that the multi-layer coating (28) can effectively isolate the subsea structure (26) and petroleum fuels, such as oil, flowing in. of the underwater structure (26). When petroleum fuel such as oil is collected from about one to two miles (1.6 to 3.2 km) below the ocean floor, the oil is very hot (e.g. around 130°C) . Sea water at this depth is very cold (eg around 4°C). The multilayer coating (28) can insulate oil during transport from below the ocean floor to above the ocean surface. The multi-layer coating (28) can insulate the oil so that the large difference in mean seawater temperature and mean oil temperature does not substantially affect the integrity of the oil. The multilayer coating (28) typically maintains a relatively high temperature of petroleum fuels, so that fuels, such as oil, can easily flow through subsea structures (26), such as tubes (12) and pipelines. The multi-layer coating (28) typically properly prevents the fuel (oil) from becoming too cold and therefore too viscous to flow, due to the temperature of the seawater. The multi-layer coating (28) also typically appropriately prevents the oil from forming waxes that act detrimentally to clog subsea structures (26) and/or form hydrates that detrimentally change the nature of the oil and also act to clog the underwater structures (26). The multi-layer coating (28) can be flexible to allow the subsea structure (26) to be manipulated in different ways. For example, the subsea structure (26) of this description, such as a pipeline, may be dropped from the edge of an oil platform, rig or ship, and maneuvered by machine, or otherwise, across the ocean and into the ocean floor. Also, if any of the subsea structures (26) is made of a swellable material, such as a metallic material, it can swell due to any of a number of factors, including heat. The flexibility of the multilayer coating (28) typically allows for swelling due to, for example, heat, without becoming delaminated. That is, the multilayer coating (28) can stretch with the expanding subsea structure (26) without deteriorating or delaminating. It should be appreciated that the multilayer coating (28) may also have applications beyond offshore oil and gas exploration, including, but not limited to, any type of submerged applications, including in freshwater and seawater.

[00112] Any one or more of the layers can be formed in situ in the subsea structure (26). Components from any one or more of the layers can be combined at the time of disposing of components in the subsea structure (26).

EXAMPLE

[00113] The example here compares a polyurethane elastomer formed in accordance with the present invention with an unformed formulation in accordance with the present invention for resistance to hydrolysis in hot salt water.

[00114] The elastomeric sample plates were produced using a “book-shaped mold”, which is an aluminum mold that has a top and bottom and is hinged on one side and open on the opposite side. The elastomeric sample plates created for evaluation were approximately 0.3175 cm thick, 25.4 cm wide, and 25.4 cm long (i.e., 1/8 inch thick, 10 inches long, and 10 inches wide). width).

[00115] For each of the elastomeric plates, the isocyanate-reactive components were weighed into a Hauschild Speedmixer beaker and then mixed using the Hauschild Speedmixer (2200 rpm, 30 seconds). The gases dissolved in the polyol mixture and the isocyanate were removed under vacuum. The required amount of isocyanate was then poured into a Speedmixer beaker and the mixture blended using the Speedmixer for approximately 40 seconds. The reaction mixture was then poured into an angled aluminum oven-heated book-shaped mold that was preheated to 80°C. The plates (25.4 cm x 25.4 cm x 0.3175 cm) (i.e. 10 inches x 10 inches x 1/8 inches) were cured in the mold at 80°C until cured sufficiently for demoulding, and then , post cured for about 18 hours at 80°C and then 160°C for one hour.

[00116] Test specimen specimens (drawbars type S2 made in accordance with DIN 53504) were cut in the mold of the post cured plates. The initial tensile strength (DIN 53504, sample type S2, crosshead speed, 200 mm/min; gauge length: 38 mm) was determined after submerging the drawbars in salt water for at least 1 month at room temperature. . The initial tensile strength was used to calculate the percentage loss in tensile strength after exposure. To assess hydrolysis resistance, the drawbars were submerged in hot synthetic seawater (ASTM D665) at 102°C using an autoclave. This method is sometimes referred to as “hot/wet aging”. The specimens were removed at predetermined times and tested (without drying) for tensile strength using the standard test method DIN 53504 S2.

Tabela 1: Formulações para exemplo 1 e comparação 1. Matérias primas para tabela 1 Poliol 1 - Resina de poli(butadieno) terminada em hidroxila (MW 2800 g/mol, OH#: 47,1, Visc.: 8000 mPa^s (23 °C). Disponível na Cray Valley como Poly bd R45HTLO. Poliol 2 - Dímero diol hidrogenado (OH# 206, MW 537 g/mol). Disponível de BASF como Sovermol 908. Extensor de cadeia - 2 etil-1,3-hexanodiol, Sigma-Aldrich. Peróxido - peróxido de dicumila, Sigma-Aldrich. Catalisador - BiCat 8118 da Shepherd Chemical Company (óleo de mamona a 10%). Agente de secagem - Molsiv 3A, UOP. Desespumante - BYK 066N, Byk Chemie. Isocianato: MDI polimérico (PMDI) (%NCO = 31,5, f = 2,7, Viscosidade = 200 mPa.s a 77°F (25°C). Disponível na BASF como Lupranate M20. Água do mar sintética - tipo ASTM D665, Sigma-Aldrich.[00117] An example of a polyurethane formulation according to the present invention is shown in table 1 (formulation amounts are parts by weight). Also shown in table 1 is comparison 1, not obtained according to the invention. Example 1 contains peroxide and was post cured at 160°C for one hour to crosslink the elastomer in accordance with the present invention. Comparison 1 does not contain peroxide (but was also post-cured at 160oC for one hour).

Table 1: Formulations for Example 1 and Comparison 1. Raw Materials for Table 1 Polyol 1 - Hydroxyl terminated poly(butadiene) resin (MW 2800 g/mol, OH#: 47.1, Visc.: 8000 mPa^s ( 23 °C) Available from Cray Valley as Poly bd R45HTLO Polyol 2 - Hydrogenated dimer diol (OH# 206, MW 537 g/mol) Available from BASF as Sovermol 908 Chain Extender - 2 Ethyl-1,3- hexanediol, Sigma-Aldrich Peroxide - dicumyl peroxide, Sigma-Aldrich Catalyst - BiCat 8118 from Shepherd Chemical Company (10% castor oil) Drying agent - Molsiv 3A, UOP Defoamer - BYK 066N, Byk Chemie. Isocyanate: Polymeric MDI (PMDI) (%NCO = 31.5, f = 2.7, Viscosity = 200 mPa.s at 77°F (25°C). Available from BASF as Lupranate M20. Synthetic Seawater - ASTM type D665, Sigma-Aldrich.

[00118] The hot/wet immersion test results for the material in table 1 are shown as graphs of percentage change in tensile strength versus immersion time in figure 4. As shown in figure 4, example 1 of this invention lost 13% of its initial tensile strength after 36 weeks immersion in synthetic seawater at 102°C (after which time the test was stopped). In contrast, Comparison 1 lost 86% of its initial tensile strength after 43 weeks of immersion under the same conditions (time after which the test was stopped). For further comparison, a commercial product used in subsea applications (Elastoshore 10060R/10002T; available from BASF Corporation of Florham Park, New Jersey) was tested under the same conditions until decomposition (4 weeks) and the results are also included in the figure. 4.

[00119] These results from Figure 4 clearly show the benefit of the present invention for resistance to hydrolysis in hot salt water. Peroxide crosslinking, as in accordance with the invention, gives the polyurethane material the best ability to maintain physical properties (monitored by tensile strength in this example) during long-term immersion in hot salt water. This accelerated test gives a good indication that polyurethane formulations in accordance with the present invention will retain important physical properties for a longer time in real subsea applications compared to a non-crosslinked polyurethane formulation.

[00120] It is to be understood that the appended claims are not limited to the express and particular compounds, compositions, or methods described in the detailed description, which may vary between particular embodiments that are within the scope of the appended claims. With respect to any Markush groups used here as a basis for describing particular features or aspects of various modalities, it should be appreciated that different, special, and/or unexpected results may be obtained from each member of the respective Markush group independently of all other Markush members. . Each member of a Markush group can be used on an individual basis and/or in combination and provides appropriate support for specific modalities within the scope of the attached claims.

[00121] It should be understood that the term medium hydroxy functionality is used when referring to a mixture of polymers, such as a mixture of a polyether polyol and a polydiene polyol.

[00122] It is also to be understood that any ranges and subranges used as a basis for describing various embodiments of the present description independently and collectively are within the scope of the appended claims, and are understood to describe and contemplate all ranges including integer values and/or fractions, even if such values are not expressly written therein. Those skilled in the art will readily recognize that the enumerated bands and sub-bands sufficiently describe and allow for various embodiments of the present disclosure, and such bands and sub-bands may be further delineated in relevant halves, thirds, quarters, fifths, and so on. Just as an example, a range “from 0.1 to 0.9” can be further delineated in a lower third i.e. from 0.1 to 0.3, a middle third i.e. from 0.4 to 0.3 0.6, and a higher third, i.e. from 0.7 to 0.9, which individually and collectively are within the scope of the attached claims, and can be used independently and/or collectively as a basis and provide support appropriate for specific modalities within the scope of the appended claims. Furthermore, with respect to language that defines or modifies a range, such as "at least", "greater than", "less than", "no more than", and the like, it should be understood that such language includes sub-ranges and/or an upper or lower limit. As another example, a range of "at least 10" inherently includes a subrange of at least 10 to 35, a subrange of at least 10 to 25, a subrange of 25 to 35, and so on, and each subrange can be used independently and/or collectively and provide appropriate support for specific modalities within the scope of the attached claims. Finally, an individual number within a described range may be used and provide appropriate support for specific embodiments within the scope of the appended claims. For example, a range “from 1 to 9” includes several individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which can be used and provide appropriate support for specific modalities. within the scope of the attached claims.

[00123] The present description has been described in an illustrative manner, and it should be understood that the terminology that has been used is intended to be in the nature of words of description rather than limitation. Obviously, many modifications and variations of the present description are possible in light of the above teachings. It is to be understood, therefore, that within the scope of the appended claims, the present description may be practiced in a manner other than that specifically described.

Claims (15)

1. Composite article, characterized in that it comprises: A. a first layer comprising a low surface energy polymer; B. a poly(meth)acrylate layer disposed on and in direct contact with said first layer, wherein said poly(meth)acrylate layer comprises a poly(meth)acrylate comprising the reaction product of at least one acrylate polymerized in the presence of an organoborane initiator; C. an epoxide layer disposed on and in direct contact with said poly(meth)acrylate layer, wherein said epoxide layer comprises an epoxide; and D. a hydrolytically resistant layer disposed on and in direct contact with said epoxide layer, wherein said hydrolytically resistant layer has an initial tensile strength as measured in accordance with standard test method DIN 53504 S2 and comprises a polyurethane elastomer hydrolytically resistant comprising the reaction product of: I.) an isocyanate component; and J.) an isocyanate-reactive component comprising a polydiene polyol having an average hydroxy functionality of not more than 3 and a number average molecular weight of 1000 to less than 2000 g/mol; reacted in the presence of (3) a curing agent for crosslinking the carbon-carbon double bonds of the polydiene polyol, wherein said hydrolytically resistant layer retains at least 80% of said initial tensile strength as measured in accordance with the standard test method DIN 53504 S2 and after submersion in standardized seawater for 24 weeks at 102°C according to ASTM D665. 2. Composite article according to claim 1, characterized in that said poly(meth)acrylate is covalently bonded to said low surface energy polymer. 3. Composite article according to claim 1, characterized in that said low surface energy polymer is selected from polypropylene, polyethylene and combinations thereof. 4. Composite article according to claim 1, characterized in that said poly(meth)acrylate is a self-polymerization product of a C1-C20 alkyl acrylate or methacrylate. 5. Composite article according to claim 1, characterized in that said poly(meth)acrylate is a reaction product of a first C1-C20 alkyl acrylate or methacrylate and a second C1-C20 alkyl acrylate or methacrylate. 6. Composite article according to claim 1, characterized in that said poly(meth)acrylate is a reaction product of a first C1-C20 alkyl acrylate or methacrylate, a second C1-C20 alkyl acrylate or methacrylate and a third C1-C20 alkyl acrylate or methacrylate. 7. Composite article according to claim 1, characterized in that said epoxide is the reaction product of an epoxy compound and an amine. 8. Composite article according to claim 1, characterized in that said organoborane initiator is additionally defined as an organoborane-organonitrogen complex. 9. Composite article according to claim 1, characterized in that said organoborane initiator is an organoborane-amine complex and said at least one acrylate is polymerized in the presence of said organoborane-amine complex and an amine-reactive compound. 10. Composite article according to claim 1, characterized in that said composite article has a peel strength of at least 8.93 kg/cm (50 pli) measured between said hydrolytically resistant layer and said epoxide layer using ASTM D6862. 14. Composite article according to claim 1, characterized in that said hydrolytically resistant layer retains at least 99% of said initial tensile strength as measured in accordance with the standard test method DIN 53504 S2 and after submersion in water of the standardized sea for 24 weeks at 102°C according to ASTM D665. 12. Method for forming a composite article as defined in claim 1, said method characterized in that it comprises the steps of providing the first layer of low surface energy polymer; providing the at least one acrylate and the organoborane initiator; provide the epoxide; providing the isocyanate component and the isocyanate-reactive component; arranging the at least one acrylate and the organoborane initiator in the first layer; polymerizing the at least one acrylate in the presence of the organoborane initiator to form the poly(meth)acrylate layer; arranging the epoxide on the poly(meth)acrylate layer, curing the epoxide to form the epoxide layer; arranging the isocyanate component and the isocyanate-reactive component in the epoxide layer; and reacting the isocyanate component with the isocyanate-reactive component in the presence of the curing agent for crosslinking the carbon-carbon double bonds of the polydiene polyol to form the hydrolytically resistant layer and multilayer coating. 13. Submarine structure, characterized in that it comprises: A. a tube having a length; B. a first layer disposed on said tube and comprising a low surface energy polymer; C. a multilayer coating disposed on and in direct contact with said first layer, wherein said multilayer coating comprises: (1) a poly(meth)acrylate layer disposed on and in direct contact with said first layer, wherein said layer of poly(meth)acrylate comprises a poly(meth)acrylate comprising the reaction product of at least one polymerized acrylate in the presence of an organoborane initiator; (2) an epoxy layer disposed on and in direct contact with said poly(meth)acrylate layer, wherein said epoxide layer comprises an epoxide; and (3) a hydrolytically resistant layer disposed on and in direct contact with said epoxide layer, wherein said hydrolytically resistant layer has an initial tensile strength as measured in accordance with standard test method DIN 53504 S2 and comprises an elastomer of hydrolytically resistant polyurethane comprising the reaction product of: (a) an isocyanate component; and (b) an isocyanate-reactive component comprising a polydiene polyol having an average hydroxy functionality of not more than 3 and a number average molecular weight of 1000 to less than 2000 g/mol; wherein said hydrolytically resistant layer retains at least 80% of said initial tensile strength as measured in accordance with standard test method DIN 53504 S2 and after submersion in standardized seawater for 24 weeks at 102°C in accordance with ASTM D665 . 14. Subsea structure according to claim 13, characterized in that the subsea structure has a peel strength of at least 8.93 kg/cm (50 pli) measured between said hydrolytically resistant layer and said epoxide layer using ASTM D6862. 15. Subsea structure according to claim 13, characterized in that said hydrolytically resistant layer retains at least 99% of said initial tensile strength as measured in accordance with the standard test method DIN 53504 S2 and after submersion in water of the standardized sea for 24 weeks according to ASTM D665.

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